Suwannee River fulvic acid (SRFA) and humic acid (SRHA) were used as dissolved organic matter (DOM) and were applied to probe the effect of DOM. Addition of DOM resulted in decreased first order rate constants for all species selected. The inhibition became more significant as the hydrophobicity of the species increased. The decrease could not be simply attributed to the binding of hydrophobic species to DOM. This can be explained by the physical isolation of iron (II), which binds to hydrophilic sites of DOM and is the hydroxyl radical generation site, from hydrophobic pollutants which bind to hydrophobic sites of DOM. Accordingly, species which could compete agains t this physical isolation by DOM and bring iron (II) closer to target species could increase the degradation rates. This was observed with application of carboxymethyl-ß-cyclodextrin (CMßCD). Effects from concentration, structure of the target species and acidity etc., were studied. The increased degradation rates were observed even in the presence of DOM. Studies on ternary complexes of hydrophobic pollutants, iron (II) and CMßCD were carried with ESMS, UV and Fluorescence experiments and further calix[6]arene derivatives. Along with the fact that CMßCD can increase the solubility of hydrophobic species and remove them from contaminated sites, this indicates a potential application to in-situ degradation systems. Initial two -phase studies were carried out with quartz sand deposited with polycholobiphenyl (PCBs) and polycyclic aromatic hydrocarbons (PAHs). Successful degradations were observed with PCBs but not PAHs. The difference is attributed to the slow equilibrium of sorbed PAHs with dissolved CMßCD and the higher PAH loading used in these experiments. A halide sensor-molecule (1, 8-diphenylureaylnaphthalene), which performs with increasing fluorescence in the presence of fluoride and decreasing fluorescence with all other halides, was synthesized and reported. Studies using NMR and computer modeling with SPARTAN were carried out to compare the sensor-molecule with an analog, 2, 3-diphenylureaylnaphthalene. Both studies indicated that only fluoride can be accommodated in the space between the urea group protons to form a strong interaction. The sensor-molecule could to lead to improved sensors that overcome limitations with current fluorescence-quenching based anion sensors.

The induction of hepatic cytochrome P4501A1 and its monooxygenase activity 7-ethoxyresorufin O- deethylase, (EROD) in fish by PAHs, PCBs and dioxins has been suggested as an early warning system &ldquo / most sensitive biochemical response&rdquo / for assessing environmental contamination conditions. In this study, the degree of induction of cytochrome P4501A1 protein as determined immunochemically and CYP1A1 associated EROD activity in fish were utilized as biomarkers of exposure to PAHs, PCBs and related organic pollutants along the izmir Bay on the Aegean Sea Coast after the Great Canal Project. Three different fish species were used throughout this study, namely leaping mullet (Liza saliens), annular seabream (Diplodus annularis) and common sole (Solea vulgaris) which were representatives of pelagic, benthopelagic and benthic fish, respectively. Fish were sampled in November 2002 and October 2003 from different sites of the Bay. The mullet caught from Harbor, &Uuml / &ccedil / kuyular port site, and Pasaport region displayed highly elevated EROD activities which were 2258&plusmn / 840 (n=15), 2011&plusmn / 490 (n=4), 1813&plusmn / 287 (n=11) pmole /min/mg protein, respectively and were 104, 80 and 79 fold higher than that of fish obtained from the reference point (25&plusmn / 9 pmole/min/mg protein / n=4). Mullet caught along the pollutant gradient at three other sites (Hekim Island, inciralti, and Zeytinalani) exhibited less but highly significant induced EROD activity. EROD activities of common sole sampled from Fo&ccedil / a open sites (107&plusmn / 20 pmol/min/mg protein, n=5) and site16A (80&plusmn / 12 pmol/min/mg protein, n=9) were found to be very low and the latter was accepted as reference site. The highest EROD activity were seen in fish captured from inciralti which was about 6.3 times higher than those obtained from reference site. Common sole caught from the mouth of Gediz River and Hekim Island exhibited also highly elevated EROD activities. Annular seabream was tested to monitor CYP1A inducing chemicals for the first time in this study. The highest EROD activity (1376&plusmn / 279 pmol/min/mg protein, n=8) were detected in fish samples collected from Harbor region. An inverse relationship was found between distance to the harbor region and EROD activities of annular seabream captured from other sampling sites. In this study for the first time, major cytochrome P450 dependent mixed function oxidase activities such as benzphetamine N- demethylase, ethylmorphine N-demethylase and aniline 4- hydroxylase, were characterized in annular seabream. Changes in the P450 1A1 protein level were determined by immunochemical analysis to monitor the pollutant based induction in all fish species and good correlation was obtained between EROD activity and CYP1A protein content. Fish from polluted sites had both highly induced EROD activity and cytochrome P450 1A content. Chemical analysis of total PAH concentration in sediment and liver tissues of some fish sample were also carried out. Although, izmir Great Canal Project has been active since 2000 to treat and protect the izmir Bay from the contamination of domestic and industrial wastes this study clearly demonstrated that the level of PAH, PCB and dioxin type persistent organic contaminants are still very high especially in the Inner and Middle Bay. This has implications for human fish consumption from contaminated areas, as well as for the health status of aquatic organisms.

Les estuaires sont des zones de transition entre les eaux fluviales et les océans soumis à de fortes contraintes d’origine anthropique, telles que la pollution chimique. Pourtant, les estuaires sont d’une importance écologique primordiale, et sont notamment des zones de nourricerie ou de reproduction pour de nombreuses espèces. Le Flet européen Platichthys flesus est un modèle souvent utilisé comme espèce sentinelle dans les estuaires. Le but de ces travaux est d’explorer les mécanismes de réponse du Flet européen à la contamination chimique, afin éventuellement d’identifier de nouveaux biomarqueurs. Il a donc été choisi de mener cette étude par une approche de protéomique par électrophorèse en deux dimensions. Les protéines différentiellement accumulées en réponse à la pollution ont été identifiées par MALDI TOF-TOF. Ces études par protéomique ont été complétées par des mesures ciblées de transcription de gènes. Tout d’abord, des flets juvéniles issus d’un élevage ont été contaminés expérimentalement avec deux doses d’un cocktail de HAP et PCB (concentration retrouvée dans la Seine, et 10 fois celle-ci). Après 29 jours de contamination, le métabolisme énergétique paraît dérégulé. Des protéines impliquées dans les défenses anti-oxydantes et la détoxification sont accumulées dans le foie des poissons contaminés. Les résultats nous ont conduit à poser l’hypothèse de l’implication de la BHMT dans un cycle aboutissant à la production de GSH, et qui pourrait donc participer à la détoxification ou aux défenses anti-oxydantes. Ensuite, les profils protéiques de foies de poissons issus de 3 estuaires de la Manche ont été comparés. Les profils protéiques des foies de poissons de la Seine et de la Tamar, 2 estuaires présentant des profils de contamination différents, se sont révélés différents des profils protéiques des foies des poissons de la Canche. Des différences moins marquées entre les profils protéiques des foies de poissons de la Seine et de la Tamar pourraient refléter les différences entre les contaminants présents dans ces estuaires. / Estuaries are important areas highly susceptible to anthropogenic degradations such as pollution. Estuarine species have to cope not only with environmental constraints inherent to estuarine habitats, but also with the presence of contaminants, the occurrence of hypoxic events or with waters warming. The European flounder Platichthys flesus is considered as a sentinel species in estuarine water quality monitoring. This study investigates the molecular mechanisms allowing the European flounder to cope with these different stress factors, both in environmental and experimental conditions, in order to eventually identify potential biomarkers of the response to contamination. A proteomic approach using 2-dimensional electrophoresis followed by MALDI TOF-TOF mass spectrometry allowed us to identify differentially expressed proteins in flounder livers, and then to better understand the mechanisms and a pathway implied in the response of flounder to environmental constraints. These observations were completed by targeted markers analyses by qPCR and enzymatic activity measurements. First, farm flounders were experimentally contaminated with two concentrations of PAH/PCB cocktails (concentrations found in the Seine and ten times this concentration). After 29 days of contamination, energetic metabolism was deregulated in contaminated flounder livers. Proteins involved in anti-oxidative defenses and detoxification were also accumulated. We suggest that BHMT could be implied in a pathway leading to the production of GSH allowing detoxification and anti-oxidative defense. Then, Flounders were fished in contrasted estuaries along the French Atlantic coast. The liver proteomic patterns of Flounders from the Seine (France) and the Tamar (UK), two estuaries displaying different contamination patterns, and from the Canche (France), were compared to characterize the proteins differentially expressed between these sites. Proteome profiles reflected the contamination patterns in each estuary.